Vat dyes

ABSTRACT

New brown vat dyes prepared by heating a compound of the formula   IN A MELT COMPRISING ANHYDROUS ALUMINUM CHLORIDE AND UREA, PYRIDINE, PICOLINE OR LUTIDINE OR A COMBINATION THEREOF, IF DESIRED, IN THE PRESENCE OF A HALOGENATING AGENT. Said dyes are suitable for dyeing various kinds of fibrous material, but as they can not be directly defined by a structural formula, they are defined by the process for preparing them.

United States Patent 91 Fujii et al.

[111 3,741,994 [451 June 26,1973

[ VAT DYES [75] Inventors: Fumio Fujii; Koji Kurahara;

. Akitoshi lgata; Nobuyoshi Abe;

Tetsuo Yamamoto, all of Omuta, Japan [73] Assignee: Mitsui ToatsuChemicals,

Incorporated, Tokyo, Japan [22] Filed: Apr. 7, 1970 [2i] Appl. No.:26,386

[30] Foreign Application Priority Data OTHER PUBLICATIONS Venkatarman,The Chemistry of Synthetic Dyes, Vol. II, Pp- 9812, (1952). v

Primary Examiner-Lorraine A. Weinberger Assistant Examiner-Robert GerstlAttorneyChristen, Sabol and O'Brien [57] 7 ABSTRACT New brown vat dyesprepared by heating a compound of the formula thereof,- if desired,inthe presence of a halogenating agent. Said dyes are suitable fordyeing various kinds of fibrous material, but as they can not bedirectly defined by a structural formula, they are defined by theprocess 'for preparing them.

13 Claims, No Drawings VAT DYES This invention relates to a new vat dyeprepared by heating a compound of the formula 1 in a melt comprisinganhydrous aluminum chloride and urea, pyridine, picoline or lutidine ora combination thereof, if desired, in the presence of a halogenatingagent and to a method of dyeing or printing fibrous materials with thedye.

The fact that fusion of a compound of the formula (1) in a mixture ofpotassium hydroxide and an alcohol at a temperature of l20200C. affordsa vat dye (C.I. Vat Black 25) which dyes cottom in olive color is knownthrough US. Pat. No. 1,845,469.

It has now been found that when a compound of the formula 1. is heatedat 50-200C. in a melt comprising anhydrous aluminum chloride and urea,pyridine, picoline or lutidine or a combination thereof, if desired, inthe presence of a halogenating agent, a new vat dye can be obtainedwhich dyes various kinds of fibrous material in fast brown to bluishbrown tint.

This dye producing brown to bluish brown tint is quite different fromthe dye (C.I. Vat Black 25) disclosed in said US. patent. As the dye ofthis invention can not be defined directly by way of a structuralformula, however, it is'difmed by the specified process for preparingsame.

The dye of this invention is prepared most preferably by heating 1 partof a compound of the formula 1 at l lO-l30C. in a melt comprising 5-10parts of anhydrous aluminum chloride and 0.1-3 parts of urea, pyridine,picoline or lutidine or an'appropriate combination thereof for severalto lO-oddhours or by heating said compound for a short period of time inthe melt to which 0.2 of a halogenating agent are added.

When pyridine, picoline or lutidine is employed in the preparation ofthis dye, the melt will decrease its viscosity and so its treatment willbecome very easy. Further, the use of a halogenating agent serves notonly to promote the reaction but also to adjust the halogen content ofthe dye, thus making change in color tone 7 of the dye. Adequate as thehalogenating agent are sulfuryl chloride, thionyl chloride, etc.

The dyes of this invention afford dyeings of excellent color value notonly by the W process which is considered to be suitable for dyeing witha conventional brown vat dye but also by the N process wherein higheralkali concentration and higher dyeing temperature are adopted. This isdue to the reason that the dyes of this invention are stable in achemical bath as compared with conventional brown dyes, and is indeedone of the excellent characteristics of the dyes of this invention.

plied to dyeing or printing of fibrous materials with the dyes of thisinvention. Applicable to the dyes of this invention are a processwherein the dye is converted into its leuco salt or vat acid with areducing agent such as sodium hydrosulfite or thiourea dioxide and thenfibrous materials are dyed or printed with such salt or acid, a processwherein the dye is previously ground together with a dispersing agentinto finely divided particles according to a usual manner and thedispersion is applied to fibrous materials and then thermofixed and aprocess wherein the dye is brought into contact with said reducing agentand reduction and fixation of the dye are simultaneously carried out onthe fibrous mate rials.

When fibrous materials are dyed with the dyes of this inventionaccording to the aforementioned dyeing processes, good reproducibledyeing can be effected without being largely affected by changes indyeing conditions.

In an ordinary dyeing operation with the dyes of this invention, theresult of dyeing is less affected by the variation of the amounts ofsodium hydrosulfite as reducing agent and sodium hydroxide, and also bya neutral salt such as sodium sulfate or sodium chloride added to thedye bath. Thus, excellent dyeing can be attained by any of the so-calledN process (This process is suitable for using a dye of strong affinity,in which dyeing is carried out at 55-60C. with a relatively large amountof sodium hydroxide. A neutral salt is not added to the dye bath.), Wprocess (This process is suitable for using a dye of weak affinity, inwhich dye ing is carried out at 45-50C. with sodium hydroxide in anamount of half as much as the amount in N process. A neutral salt isadded to the dye bath to enhance exhaustion.) and K process (Thisprocess is suitable for using a dye of weaker affinity, in which dyeingis car ried out at 2025C. with sodium hydroxide in an amount smallerthan that in W process. The amount of a neutral salt to be added to thedye bath is larger than that in W process).

Likewise, in the case of applying a pad steam continuous dyeing, theresult of dyeing is less influenced by change in the quantities ofsodium hydrosulfite, sodium hydroxide, hydrogen peroxide and sodiumperborat used.

The dyeings obtained according to this invention possess variouscharacteristics. First, the dyeings having extremely good colorrendering (extremely low color change under various illumination s),i.e. a very slight differencebetween the color tone under the standardillumination of colorimetry C (daylight) and the color tone under theillumination A (illumination similar to tungsten a'rc lamp at night).Although the dyeings dyed with Threne Brown R which is comparativelysimilar to color tone to the dyes of this invention look reddish or-.ange under the illumination A, the dyes of this'invention do not showsuch color change.

It is also one of the characteristics of the dyes of this, inventionthat they possess weak intensity of reflection n 'on radiation ofinfra-red rays which has begum to be watched recently.

As other characteristics, the dyeings with the dyes of this inventionhas various kinds of good fastness, especially excellent fastness toresin treatment.

fibers. in addition, the dyes of this invention also have affinity forpolyester fibers which have not been dyed with known vat dyes, whenemployed according to the thermosol method. In case mixed spun fiber ofcottom and polyester is dyed according to the thermosol method using thedyes of this invention, therefore, using a dye for the polyester fibertogether will not particularly be necessary.

Thus, the effect or merit achieved by this invention is especiallyremarkable.

This invention will be illustrated by the following examples wherein allparts are by weight.

EXAMPLE 1 A mixture of 150 parts of anhydrous aluminum chloride, 30parts of picoline and 3 parts of sulfuryl chloride was heated at140-l50C. to melt. To this melt were added at 120C. parts of a compoundof the formula 1 and the whole was stirred for 1 hour at l25-l30C. Themelt was then poured into 2000 parts of water containing parts ofconcentrated hydrochloric acid and the precipitate formed was filteredand washed with water until the filtrate became neutral to obtain 13.5parts of a dye containing 1.7 percent chlorine.

0.1 Part of this dye was wetted with 1 part of ethanol and 100 parts of50C. were added. Four Parts of 30 percent aqueous solution of sodiumhydroxide and 0.8 part of sodium hydrosulfite were added and reductionwas carried out at 60C. for 15 minutes to dissolve the dye. To thissolution were further added 3 parts of sodium sulfate and water of 50C.in an amount to make the whole to 200 .parts to prepare a dye bath.

Ten Parts'of cottom were dipped into the dye bath, maintained at 50C.for 30 minutes, squeezed off and then subjected to oxidation and soapingto effect dyeing. The resulting dyeings in brown tint showed variouskinds of fastness in the tests described below. (JIS means JapanIndustrial Standard) Tests for fastness:

Light JIS L-l044-l959 (carbon arc lamp) Washing .IIS L-lO45-l959 (MC-3)Bleaching with hypochlorite .llS L-0856-l967 (strong) (effectivechlorine 2g./l

EXAMPLE 2 A mixture of 150 parts of anhydrous aluminum chloride and 30parts of urea was molted at 200C. and 3 parts of sulfuryl chloride wereadded thereto at l 10C. 15 parts of a compound of the formula 1 werethen added and the whole was stirred for 1 hour at l-l C. The melt wasthen worked up as described in Example 1 to obtain 16.8 parts of a dyecontaining 2.8 percent chlorine.

This dye was incorporated with Demol N (trade name of a product marketedby Kao Sekken K.K. as a dispersing agent) and ground into fineparticles. 0.4 Part of the dispersed dye thus obtained was dispersed at25C. into 50 parts of water and then 3 parts of 30 percent aqueoussolution of sodium hydroxide and 2 parts of Rongalit C were added. Thewhole was diluted to 200 parts with water of 25C.

Ten Parts of cottom yarn were dipped into the dye bath and, afterelevating the temperature to C. in the course of 10 minutes, 3 parts ofsodium sulfate were added thereto. The temperature of the dye bath wasthen raised to -100C. in the course of 15 minutes and the yarn wasmaintained at this temperature for 10 minutes and thereafter subjectedin a usual manner to oxidation and soaping to effect dyeing.

The resultant dyeings in brown tint had good fastness to sunlight,washing, etc.

EXAMPLE 3 A mixture of 150 parts of anhydrous aluminum chloride and 30parts of urea was molten at 200C. and 15 parts of a compound of theformula 1 were added at l25-l 30C. The melt was stirred for 4 hours andthen worked up as described in Example 1 to obtain 15.8 parts of a dyecontaining 0.4 percent chlorine.

This dye was ground into fine particles as described in Example 2 and0.4 part of the finely ground dye was dispersed into 200 parts of waterkept at 25C. Into this dye dispersion were dipped 10 parts of rayonstaple yarn for 5 minutes and thereafter 3 parts of 30 percent aqueoussolution of sodium hydroxide and 0.6 parts of sodium hydrosulfite wereadded. The temperature of the dye bath was raised to 50-55C. in thecourse of 15 minutes and 3 parts of sodium sulfate were added. The yarnwas maintained at this temperature for 20 minutes, squeezed off and thensubjected in a usual manner to oxidation and soaping to effect dyeing.The resulting dyeings were brown in tint and had good fastness.

EXAMPLE 4 The dye prepared in Example 3 was ground into fine particlesas described in Example 2 and 2 parts of the finely ground dye weredispersed into 50 parts of water of 25C. 10 parts of a 1 percent aqueoussolution of sodium alginate were added to the dispersion and then waterin an amount sufficient to make the whole to parts was added to preparea dye dispersion. Cotton cloth was padded at 30C. in the dispersion,uniformly squeezed off by the aid of a roller, half-dried at C. for 3minutes and wound on a jigger. The cloth was then wound off and upreciprocally several times in a chemical liquor bath of the compositionshown below which was used in an amount of 5 times as much as the weightof the cloth, whereby reduction of the dye was effected. The cloth wasthen subjected to oxidation and soaping in a usual manner to finishdyeing. Asa result, the dyeings in brown tint having good fastnesswere-obtained. 1

The composition of the chemical liquor (per liter): 30 aqueous solutionof sodium hydroxide 30 cc sodium hydrosulfite 8 g. sodium sulfate 30 g.

EXAMPLE 5 A mixture of parts of anhydrous aluminum chloride, 37 parts ofurea and 2.5 parts of picoline was molten at l40-150C. 1.8 Parts ofthionyl chloride were added at 1 C. and then 20 parts of a compound ofthe formula 1 were added. The melt was stirred for 2 hours at l25l 30C.and then worked up as described in Example 1 to obtain 20.7 parts of adye containing 2.6 percent chlorine.

This dye was finely divided together with Demol N and then treated asdescribed in Example 4 to prepare a dye dispersion. Cotton cloth waspadded in the dye dispersion at 30C., uniformly squeezed off by the aidof a roller, half-dried at l0O-l 10C for 3 minutex, again padded at 30C.in a bath containing each 30 g. of sodium hydroxide, sodiumhydrosulfi'te and sodium chloride in 1000 parts of water, uniformlysqueezed off and immediately subjected to steaming for 35 seconds insaturated steam at l00-l02C. to effect coloration and then" to oxidationfollowed by soaping. The resultant dyeings were brown in tint and hadgood fastness.

EXAMPLE 6 The dye obtained in Example l was finely divided as describedin Example 2 and 5 parts of the resulting paste of the dye weredispersed in 5 parts of water of 25C. Ninety Parts of a paste were addedto the dispersion to prepare a coloring thickening. Cotton cloth-wasprinted with the coloring thickening and, after drying, the printedareas were overprinted by means of a blotch roller with a chemicalthickening having the composition shown below and then subjected tosteaming for 35 minutes in saturated steam at l00-l02C. The cloth wassubsequently subjected to washing with water, oxidation soaping tofinish printing. The dyeings in brown tint having good fastness werethus obtained.

The composition of the chemical thickening thickening agent 65 30percent aqueous solution of sodium hydroxide 27 sodium hydrosulfite 8EXAMPLE 7 A mixture of 150 parts of anhydrous aluminum chloride and 30parts of picoline wasmolten at 140-l 50C. and parts of a compound of theformula 1 were added at 130l35C. The melt was stirred at the sametemperature for 2.5 hours and then worked up as described in Example 1to obtain 14.6 parts of a dye containing 0.4 percent chlorine.

This dye was finely ground as described in Example 2 and 5 parts of theresulting paste of the dye were dispersed into 10 parts of water of 25C.85 Parts of a thickening having the composition shown below were addedto the dispersion to prepare a coloring thickening.

Cotton cloth was printed with the coloring paste and, after drying,subjected to steaming at l00-l20C. for 10 minutes in saturated steam,washing with water, oxidationand soaping to finish printing. The dyeingsthus obtained was bluish brown in tint and had good fastness.

The compositionof the thickening:

thickening agent 50 parts water 5 parts glycerol 8 parts potassiumcarbonate 12 parts Rongalit C 10 parts EXAMPLE 8 7 Cotton cloth wasprinted with a cloring thickening containing the finely ground dyeprepared in Example 6 3 and having the under-mentioned composition andthen dried at C. The cloth wassubjected successively to steaming for 10minutes at 100- 102C. with saturated steam, washing with water,oxidation and then soaping to obtain the dyeings in brown tint havinggood fastness. 1

The composition of the coloring paste the finely ground dye 2 glycerol 4British gum thickening (1:1) 60 1 40 Be sodium hydroxide solution 4sodium hydrosulfite 2 potassium carbonate 8 water 8 Rongalit C (1:1) 12EXAMPLE 9 Using the dye of Example 7, a dye dispersion was prepared asdescribed in Example 4. Polyester fabricwas padded at 30C. with the dyedispersion, uniformly squeezed off by the aid of a roller and half-driedat l001 10C. for 3 minutes. The fabric was then treated in a drier at200C. for 2 minutes and subjected to soaping to effect dyeing. Thedyeings thus obtained were bluish brown in tint and had good fastness.

EXAMPLE 10 Using a finely ground dye obtained by treating the dyeprepared in Example 1 in a manner similar to that described in Example2, polyester fiber/cotton mixed spun fabric was treated by the thermosolmethod according to Example 9 and then subjected to pad steam dyeing asdescribed in Example 5 to obtain the dyeings in which polyester fiberand cottom were dyed in brown tint of the same strength.

0.1 Part of the dye obtained in Example 5 was wetted with 1 part ofethanol. To the wetted dye were added 50 parts of water of C. and 2parts of a 30 percent aqueous solution of sodium hydroxide. 0.6 Part ofsodium hydrosulfite was then added and the temperature was maintained at55C. for 15 minutes to effectreduction ofthe dye. One thousand Parts ofwater kept at 25C. and 1 part of Demol N were added and the mixture wasneutralized to pH 7 with acetic acid to prepare a dispersion of the vatacid. Water was added to the dis persion to adjust the total amount to200 parts. 10 Parts of cotton were dipped into the dispersion, uniformlysqueezed off, treated at C. for 10 minutes in 200 parts of a chemicalliquor of the under-mentioned composition and then subjected tooxidation followed by soaping whereby dyeing of the cotton was effected.

, The dyeings thus obtained were brown in tint and had good fastness. v

The composition of the chemical liquor (per liter)? 30 percent aqueoussolution of sodium hydroxideiS sodium hydrosulfite 0.5 g.

sodium sulfate 20 g.

EXAMPLE 12 A mixture of 150 parts of anhydrous aluminum chloride, 37parts of urea and 2.5 parts of pyridine was heated at l40-l50C. to melt.1.8 Parts of thionyl chloride were added at C. to the mixture and then20 parts ofa compound of the formula 1 were added and the whole wasstirred for 2. hours at -.l30C. The melt was treated in a manner similarto that described in Example l to obtain 21 parts of a dye containing2.6 percent chlorine.

One part of this dye was wetted with parts of ethanol. To the wetted dyewere added 60 parts of water of 55C. and 8 parts of a 30 percent aqueoussolution of sodium hydroxide. 2 Parts of sodium hydrosulfite was thenadded, while the temperature was maintained at 55C., and reduction ofthe dye was carried out for minutes. Twenty Parts of water and 1.5 partsof Demol N were added and the mixture was neutralized to pH 7 withacetic acid. Water was then added to the mixture 'to adjust the totalquantity to 100 parts whereupon a ner to oxidation and soaping to finishdyeing. The dyeings thus obtained were brown in tint and had goodfastness.

The composition of the chemical liquor (per liter): 30 aqueous solutionof sodium hydroxide 10 cc sodium hydrosulfitc 2 g. sodium sulfate 30 g.

EXAMPLE 13 Cotton cloth was padded with 1000 parts of a dispersion ofthe vat acid of Example 12, to which 1 part of sodium alginate had beenadded, and then half-dried at 100C. for 3 minutes. The cotton cloth wasagain padded at 30C. with 1000 parts of a chemical liquor containingeach parts of sodium hydroxide, sodium hydrosulfite and sodium chloride,uniformly squeezed off and immediately subjected to steaming for 40seconds in saturated steam at 100C., whereby coloration was effected.The cloth was then brought to oxidation and soaping, and thus thedyeings in brown tint having good fastness were obtained.

EXAMPLE l4 A mixture of 150 parts of anhydrous aluminum chloride, partsof lutidine and 3 parts of sulfuryl chloride was heated at 140150C. forma melt. Fifteen Parts of a compound of the formula 1 were added at 120C.and the mixture was stirred for 1 hour at l25l30C. and worked up asdescribed in Example 1 to obtain 15.3 parts of a dye containing 1.7percent chlorine.

This dye was treated in a manner similar to that described in Example 4to prepare a dispersion of the dye. Cotton cloth was padded at 30C. withthe dye dispersion and then passed at 95C. through a chemical liquor ofthe under-mentioned composition to effect reduction of the dye andwashed with water. The cloth was then subjected successively tooxidation, washing with water, soaping, washing with water and thendrying to obtain the dyeings in brown tint having good fastness. Thecomposition of the chemical liquid (per liter): 30 aqueous solution ofsodium hydroxide 30 cc sodium hydrosulfite 6 g.

EXAMPLE 15 0.2 Part of the dye obtained in Example 2 was wetted with 1part of Turkey red oil. 47 Parts of water and 1.5 parts of 30 percentaqueous solution of sodium hydroxide were added and the mixture washeated at 55C. To this mixture was added 06 part of hydrosulfiteandreduction of the dye was effected at this What is claimed is:

l. A method for obtaining a dye which comprises heating 1 part of acompound of-the formula in a melt comprising from 5 to ID partsanhydrous aluminum chloride and from 0.1 to 3 parts of a memberselectedfrom the group consisting of urea, pyridine, picoline, lutidineand mixtures thereof for from about 1 to 10 hours at a temperature offrom 50 to 200C, and separating the dye from said melt.

2. A method according to claim 1 wherein the melt contains urea.

3. A method according to claim 1 wherein the melt contains picoline.

4. A method according to claim 1 wherein the heating is conducted at atemperature of from C to C.

5. A dye obtained according to the process of claim 1.

6. A method according to claim 1 wherein the melt contains up to 0.2parts of a halogenating agent.

7. A method according to claim 6 wherein the heat ing is conducted at atemperature of from ll0C. to 130C.

8. A method according to claim 6 wherein the melt contains picoline andthe halogenating agent is sulfuryl chloride.

9. A method according to claim 6 wherein the melt contains urea and thehalogenating agent is sulfuryl chloride.

10. A method according to claim 6 wherein the melt contains urea andpicoline and the halogenating agent is thionyl chloride. 7

11. A method according to claim 6 wherein the melt contains urea andpyridine and the halogenating agent is thionyl chloride.

12. A method according to claim 6 wherein the melt contains lutidine andthe halogenating agent is sulfuryl chloride.

13. A dye obtained according to the process of claim 6.

l II 0! t

2. A method according to claim 1 wherein the melt contains urea.
 3. Amethod according to claim 1 wherein the melt contains picoline.
 4. Amethod according to claim 1 wherein the heating is conducted at atemperature of from 110*C to 130*C.
 5. A dye obtained according to theprocess of claim
 1. 6. A method according to claim 1 wherein the meltcontains up to 0.2 parts of a halogenating agent.
 7. A method accordingto claim 6 wherein the heating is conducted at a temperature of from110*C. to 130*C.
 8. A method according to claim 6 wherein the meltcontains picoline and the halogenating agent is sulfuryl chloride.
 9. Amethod according to claim 6 wherein the melt contains urea and thehalogenating agent is sulfuryl chloride.
 10. A method according to claim6 wherein the melt contains urea and picoline and the halogenating agentis thionyl chloride.
 11. A method according to claim 6 wherein the meltcontains urea and pyridine and the halogenating agent is thionylchloride.
 12. A method according to claim 6 wherein the melt containslutidine and the halogenating agent is sulfuryl chloride.
 13. A dyeobtained according to the process of claim 6.